Amides



Patented Nov. 20, 1945 2,389,453 mamas John Harold Perrine, ProspectPark, Pa., assignor to Sun Oil Company, Philadelphia, Pa., a corporationof New Jersey No Drawing. Application April 15, 1943,

Serial No. 483,171

4. Claims.

amides, having commercially valuable properties. The amides inaccordance with this invention are those formed from a group or mixtureof saturated acids containing cycloaliphatic rings and having thegeneric formula Calla-=02, in which n has a value between 13 and 30 anda: has a value between 4 and 10. More specifically the amides are thoseformed from a group or mixture of said acidsa large proportion, andusually most, of which individually have the generic formula Cullen-:02,in which 11. may vary from 13 to 30 and a: is an even number from 4 to10. Still more fspecifically the amides are those formed from a roup ormixture of said acids which are derived, in various ways, frompetroleum.

The acids forming the group in question are obtainable from petroleumand are present, for example, as alkali salts in the asphaltic stillbottoms produced in the distillation of topped crude in the presence ofcaustic soda to produce lubricating oils '(see Pew Patent 1,761,153 andAngstadt Patent 1,931,880). tained commercially from the source as amixture of the various acids by treatment of the still bottoms with amineral acid to convert the alkali salts to free acids, followed bydistillation to obtain the acids as a distillate fraction.

The acids are also obtainable from lubricating oil fractions ofnaphthenic base crudes distilled without the addition of caustic soda.

The acids are also obtainable from gas oil fractions distilled from GuiCoastal (and probably other) crudes. Such acids may be so recovered by,for example, the process disclosed in the application of McCorquodale,Magill and Easy. Serial No. 475,318, filed February 9, 1943. 50 to 70per cent. of these gas oil acids are identical with acid obtainable fromthe still residue. Since such method for recovering the starting acidsforms no part of the present invention, its description is unnecessary.

The starting acids also appear to be obtainable by oxidation ofnaphthenic oils, as, for example, by methods similar to that disclosedin the'application of Johnson and Bruun, Serial No. 415,910, filedOctober 21, 1941.

It may be. also, that acids of the class defined may be synthesized frompure compounds by (possibly) some known method or by some process thatmay be hereafter developed.

From a practical or commercial standpoint,

however, the starting acids may be said to be those either naturallyoccurring in petroleum, or which are formed in petroleum during conven-(Cl. 260-55'l) The invention is directed to a new class of" These may beobtional processes of refining or which may be produced from petroleumby some special process.

The mixture of acids may be separated into more or less pure individualacids by fractional distillation in vacuo. The acids distill betweenabout 125 C.- and-330 C. at 2 mm. The commercial mixture solidifies atabout 50 C. However produced, the mixture of acids will generallycontain some hydrocarbons as impurities, reducing the acid number of themixture, but the presence of these hydrocarbons does not generallyprevent the use of the commercial mixture of acids inaccordance with thepresent invention.

It has been found that valuable industrial products may be obtained bytreatment of the acids comprising this group, either in purified form oras the commercial mixture, with urea for the formation of their amides,

.In general the reaction between the petroleum acids and urea will becarried out at a temperature of 150 C. to 200 0., at atmosphericpressure, or at higher temperatures at superatmospheric pressure. Thereaction will take from 10 to 20 hours at the temperature range given,less at higher temperatures under pressure. Optimum proportions ofreactants are two moles of acid to one mole of urea. Details or apreferred procedure may be found in the DAlelio Patent No. 2,109,941.

' The amide or mixture (if-amides formed in the reaction may be purifiedby water-washing and drying the reaction product. or the unreacted ureamay be removed by filtering the crude reaction product through glasswool at a temperature just below the melting point of urea. The ureawill crystallize on the glass wool. Impurities such as CO: and water canbe removed from v the product b mild heating in vacuo.

Thus, 126 g. of petroleum acids having an acid number of may be heatedwith 12 g, of urea in a sealed glass bomb tube at C. for 15 hours, Thebomb tube may then be allowed to cool to room temperature, furthercooled to about 0 C. to reduce gas pressure within the tube, and

ent invention. Thus, the acid chlorides or esters of the petroleum acidsmay be reacted with ammonia to form amides; the ammonium salt of theacids may be dehydrated at 100 C.-200' 0.: or

mamidesoipetrolcumacidsinaccordancewith this invention are viscousliquids, the properties oiwhich have not yet been fully investisated.They have the aroup formula crinza-z-icom where n and :2: have the samevalues given above for the acids, and. like the acids, are probablycharacterised by the presence 0! five-membe'red' rings.

Among other uses as intermediates, etc., the amides oi the presentinvention are valuable modifiers for use in production oi modified alkydresins. Thus extremely satisfactory synthetic resins for use in lacquersma be formed by heatin: together for one to two hours at about 225 C. 1part by weight glycerine, 2 parts phthalic anhydride, and 2 parts of theamides produced from hydrocarbon-tree petroleum acids havin: asaponiflcation number of 1'10.

This application is a continuation in part c! an application filed byme- January 15, 1941, Ser. No. 374,557.

What I claim and desire to protect by Letters Patent is:

1. The mixture or amides iormed irom a mixture of saturatedmonocarboxylic acids containin from two to five cycloaliphatic rings peraaeaasa hasavalueransinsiromewhenthenumber of cycloaliphatic rinse istwo to 10 when the number 0! oycloaliphatlc 111188 is five.

2. The mixture 01 amides Iormed from a mixture of saturatedmonocarboxylic acids containin: from two to five cycloaliphatic ringsper molecule and havin: the generic formula cant-=01 3. The mixture ofamides formed from a mixture oi saturated monocarbosylie acidscontaining from two to five cycloallphatic rinss 'per moleculeindividual acids of which have the generic formula Came-s02, wherein nis a number from 13 to 30 inclusive and a: an even number ranging (mm 4when the number of cycloaliphatic rings is 2 to 10 when the number ofcycloaliphatic rings is 5 inclusive.

4. The mixture of amides formed from a mixture of saturatedmonocarboxylic acids containins from two to five cycloaliphatic ringsper molecule individual acids of which have the generic formulacant-:02, wherein n is a num-

